TWI529251B - Magnesium alloy sheet and method of manufacturing the same - Google Patents
Magnesium alloy sheet and method of manufacturing the same Download PDFInfo
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- TWI529251B TWI529251B TW100141646A TW100141646A TWI529251B TW I529251 B TWI529251 B TW I529251B TW 100141646 A TW100141646 A TW 100141646A TW 100141646 A TW100141646 A TW 100141646A TW I529251 B TWI529251 B TW I529251B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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Description
本發明係關於適用於電氣、電子機器類的框體等的各種構件之材料的鎂合金板、及其製造方法。特別是關於具有優良的耐蝕性鎂合金板、及其製造方法。The present invention relates to a magnesium alloy sheet which is applied to materials of various members such as a frame of an electric or electronic device, and a method for producing the same. In particular, it relates to a magnesium alloy sheet having excellent corrosion resistance and a method for producing the same.
在鎂中含有各種添加元素之鎂合金，被利用在手機、個人用筆記型電腦等之攜帶用電氣、電子機器類的框體、汽車用零件等的各種構件之構成材料。A magnesium alloy containing various kinds of added elements in magnesium is used as a constituent material of various members such as a casing for electric appliances and electronic equipment such as a mobile phone or a personal notebook computer, and parts for automobiles.
由鎂合金所構成的構件，係以壓鑄法、半固態熔射(Thixomolding)法等所製作之鑄造材(ASTM規格的AZ91合金)為主流。近年，逐漸使用對由ASTM規格的AZ31合金中所代表的展延用鎂合金所構成之板實施沖壓加工而成之構件。例如，在專利文獻1，提案有由與ASTM規格之AZ91合金相當的合金所構成，具有沖壓加工性之鎂合金板。The member made of the magnesium alloy is mainly made of a cast material (AZ91 alloy of ASTM standard) produced by a die casting method or a semi-solid melting method. In recent years, a member obtained by press-forming a plate made of a magnesium alloy for extension represented by an ASTM-size AZ31 alloy has been gradually used. For example, Patent Document 1 proposes a magnesium alloy sheet which is composed of an alloy equivalent to the AZ91 alloy of the ASTM specification and has press workability.
由於鎂為活性金屬，故，在上述構件、或其材料之鎂合金的表面，一般實施有陽極氧化處理、化成處理等之防蝕處理。Since magnesium is an active metal, an anti-corrosion treatment such as anodizing treatment or chemical conversion treatment is generally performed on the surface of the above-mentioned member or a magnesium alloy thereof.
[專利文獻1]日本特開2007-098470號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-098470
在上述的AZ31合金、AZ91合金等的含有Al之鎂合金，具有Al的含有量越多、則耐蝕性越優良的傾向。例如，AZ91合金，在鎂合金中具有優良的耐蝕性。但，即使為AZ91合金，也無法充分地解決耐蝕性的問題，需要進行上述防蝕處理。在未實施有防蝕處理之情況，即使為AZ91合金，當進行鹽水噴霧實驗、鹽水浸漬實驗等的腐蝕實驗時，腐蝕會行進。又，即使為了耐蝕性的提升等作為目的，除了上述防蝕處理，另外再進行塗佈之情況，當因衝撃等造成在塗裝上產生傷痕或因小時劣化等造成塗裝剝落時，腐蝕會從鎂合金露出的部分行進。因此，期望構成鎂合金構件之鎂合金板本身具有優良的耐蝕性。In the magnesium alloy containing Al such as the above-mentioned AZ31 alloy or AZ91 alloy, the higher the content of Al, the more excellent the corrosion resistance. For example, AZ91 alloy has excellent corrosion resistance in magnesium alloys. However, even in the case of the AZ91 alloy, the problem of corrosion resistance cannot be sufficiently solved, and the above-described anticorrosive treatment is required. In the case where the anti-corrosion treatment is not carried out, even in the case of the AZ91 alloy, when a corrosion test such as a salt spray test or a salt water immersion test is performed, the corrosion proceeds. In addition, for the purpose of improving the corrosion resistance and the like, in addition to the above-described anti-corrosion treatment, when the coating is further applied, when the coating is scratched due to squeezing or the like, or peeling off due to deterioration of the hour or the like, the corrosion is caused. The exposed portion of the magnesium alloy travels. Therefore, it is desirable that the magnesium alloy sheet constituting the magnesium alloy member itself has excellent corrosion resistance.
本發明係有鑑於上述事情而開發完成的發明，其目的係在於提供具有優良的耐蝕性鎂合金板、及其製造方法。The present invention has been made in view of the above circumstances, and an object thereof is to provide a magnesium alloy sheet having excellent corrosion resistance and a method for producing the same.
本發明者們精心研究的結果，發現具有特定組成之鎂合金板可顯示優良的耐蝕性，而完成了本發明。As a result of intensive studies by the present inventors, it has been found that a magnesium alloy sheet having a specific composition can exhibit excellent corrosion resistance, and the present invention has been completed.
本發明的鎂合金板係由含有添加元素之鎂合金所構成的。又，在板中，含有添加元素及Mg之金屬間化合物的粒子分散存在著。又，板表面的XRD分析之金屬間化合物的主繞射面(4,1,1)繞射強度除以Mg合金相的c面(0,0,2)繞射強度之比率為0.040以上。The magnesium alloy sheet of the present invention is composed of a magnesium alloy containing an additive element. Further, in the plate, particles containing an intermetallic compound of an additive element and Mg are dispersed. Further, the ratio of the diffraction intensity of the main diffraction surface (4, 1, 1) of the intermetallic compound of the XRD analysis on the surface of the sheet divided by the diffraction intensity of the c-plane (0, 0, 2) of the Mg alloy phase was 0.040 or more.
本發明的鎂合金板具有優良之耐蝕性的理由，應為包含添加元素(例如，Al)及Mg之金屬間化合物(代表例為Mg17Al12)的存在狀態有密切關係，且，板表面的XRD分析之金屬間化合物的主繞射面(4,1,1)繞射強度與Mg合金相的c面(0,0,2)繞射強度之比率(金屬間化合物的主繞射面(4,1,1)繞射強度/Mg合金相的c面(0,0,2)繞射強度)在0.040以上時可發揮充分作用。再者，在本發明，鎂合金係含有50質量%以上之Mg。The magnesium alloy sheet of the present invention has excellent corrosion resistance, and should be closely related to the existence state of an intermetallic compound (for example, Mg 17 Al 12 ) containing an additive element (for example, Al) and Mg, and the surface of the sheet XRD analysis of the ratio of the diffraction intensity of the main diffraction surface (4,1,1) of the intermetallic compound to the c-plane (0,0,2) diffraction intensity of the Mg alloy phase (the main diffraction plane of the intermetallic compound) (4, 1, 1) The diffraction intensity / the c-plane (0, 0, 2) diffraction intensity of the Mg alloy phase can be sufficiently exerted at 0.040 or more. Furthermore, in the present invention, the magnesium alloy contains 50% by mass or more of Mg.
以下，說明關於本發明的鎂合金板。Hereinafter, a magnesium alloy sheet according to the present invention will be described.
構成鎂合金板之鎂合金，可舉出含有添加元素之各種組成者(殘餘部分：Mg及不純物)，但，在本發明，使用含有作為添加元素之3.0質量%~11.0質量%的Al之Mg-Al系合金為佳。Al的含有量越多，則不僅具優良的耐蝕性，且亦具有優良的強度、耐塑性變形性之機械特性的傾向。又，藉由含有Al，當製造鎂合金板時，能夠析出作為析出物之包含Al及Mg之金屬間化合物(β相)的粒子。另外，當Al的含有量過多時，則會有導致塑性加工性的降低之虞。Al的含有量係8.3質量%~9.5質量%為更佳。The magnesium alloy constituting the magnesium alloy sheet includes various components (residual portions: Mg and impurities) containing the additive element. However, in the present invention, Mg containing 3.0% by mass to 11.0% by mass of Al as an additive element is used. -Al alloy is preferred. The higher the content of Al, the better the corrosion resistance and the mechanical properties of excellent strength and plastic deformation resistance. Further, when Al is contained, when a magnesium alloy sheet is produced, particles of an intermetallic compound (β phase) containing Al and Mg as precipitates can be precipitated. Further, when the content of Al is too large, there is a possibility that the plastic workability is lowered. The content of Al is preferably 8.3% by mass to 9.5% by mass.
作為Al以外的添加元素，可舉出例如從Zn、Mn、Si、Ca、Sr、Y、Cu、Ag、Zr、Ce、Be及稀土類元素(除了Y、Ce)所選擇之1種以上的元素。在含有這些元素之情況，其含有量係總計0.01質量%以上10質量%以下為佳，0.1質量%以上5質量%以下為更佳。又，稀土類元素係含有0.1質量%以上為佳，其中，Y係含有0.5質量%以上為佳。更具體的Mg-Al系合金，可舉出例如，ASTM規格之AZ系合金(Mg-Al-Zn系合金，Zn：0.2～1.5質量%)、AM系合金(Mg-Al-Mn系合金，Mn：0.15～0.5質量%)、Mg-Al-RE(稀土類元素)系合金、AX系合金(Mg-Al-Ca系合金，Ca：0.2～6.0質量%)、AJ系合金(Mg-Al-Sr系合金，Sr：0.2～7.0質量%)等。特別是含有8.3質量%～9.5質量%之Al、0.5質量%～1.5質量%之Zn的Mg-Al-Zn系合金，代表合金為AZ91合金，在優良的耐蝕性的這一點上為佳。作為不純物，可舉出例如，Fe、Ni、Cu等。Examples of the additive element other than Al include one or more selected from the group consisting of Zn, Mn, Si, Ca, Sr, Y, Cu, Ag, Zr, Ce, Be, and rare earth elements (excluding Y and Ce). element. When these elements are contained, the content thereof is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less. Further, the rare earth element is preferably contained in an amount of 0.1% by mass or more, and preferably Y is contained in an amount of 0.5% by mass or more. More specific examples of the Mg-Al-based alloy include an AZ-based alloy (Mg-Al-Zn-based alloy, Zn: 0.2 to 1.5% by mass) and an AM-based alloy (Mg-Al-Mn-based alloy). Mn: 0.15 to 0.5% by mass), Mg-Al-RE (rare earth element)-based alloy, AX-based alloy (Mg-Al-Ca-based alloy, Ca: 0.2 to 6.0% by mass), and AJ-based alloy (Mg-Al) -Sr-based alloy, Sr: 0.2 to 7.0% by mass). In particular, the Mg-Al-Zn alloy containing 8.3% by mass to 9.5% by mass of Al and 0.5% by mass to 1.5% by mass of Zn represents that the alloy is an AZ91 alloy, and is excellent in excellent corrosion resistance. Examples of the impurities include Fe, Ni, Cu, and the like.
在本發明，具有金屬間化合物的粒子分散存在於板中之組成。作為，在由含有作為添加元素的Al之鎂合金所構成的情況，代表性金屬間化合物為包含Al及Mg之Mg17Al12。In the present invention, the particles having the intermetallic compound are dispersed in the composition of the sheet. In the case of being composed of a magnesium alloy containing Al as an additive element, a representative intermetallic compound is Mg 17 Al 12 containing Al and Mg.
在本發明，板表面的XRD分析之金屬間化合物(Mg17Al12等)的主繞射面(4,1,1)繞射強度除以Mg合金相的c面(0,0,2)繞射強度之比率為0.040以上。此比率大較好，0.055以上為更佳，0.060以上為最佳。此比率的上限未特別限定，但從實用性製造上的觀點來看，理想為0.10。In the present invention, the diffraction diffraction intensity of the main diffraction surface (4, 1 , 1) of the intermetallic compound (Mg 17 Al 12 or the like) by XRD analysis on the surface of the sheet is divided by the c-plane (0, 0, 2) of the Mg alloy phase. The ratio of the diffraction intensity is 0.040 or more. This ratio is preferably large, preferably 0.055 or more, and most preferably 0.060 or more. The upper limit of the ratio is not particularly limited, but is preferably 0.10 from the viewpoint of practical production.
使用於XRD分析之裝置的具體例、及分析條件詳細如後述。Specific examples of the apparatus used for XRD analysis and analysis conditions will be described later in detail.
在本發明，板剖面的SEM觀察之金屬間化合物(Mg17Al12等)的面積比率為10.0%以上為佳。在此，面積比率係為以百分率(%)表示金屬間化合物的總和面積對板剖面的SEM觀察之觀察視野面積之比例。面積比率大較好，10.5%以上為更佳，10.6%以上為最佳。面積比率的上限未特別限定，但，從實用的製造上觀點來看，理想為15%。In the present invention, the area ratio of the intermetallic compound (Mg 17 Al 12 or the like) observed by SEM of the cross section of the sheet is preferably 10.0% or more. Here, the area ratio is a ratio (%) indicating the ratio of the total area of the intermetallic compound to the observation field area of the SEM observation of the cross section of the sheet. The area ratio is much better, 10.5% or more is better, and 10.6% or more is the best. The upper limit of the area ratio is not particularly limited, but is preferably 15% from the viewpoint of practical production.
在本發明，金屬間化合物(Mg17Al12等)的粒子含有縱橫比未滿2的球狀粒子為佳。在此，縱橫比係以粒子的長徑與短徑之比(長徑/短徑)來表示。特別是含有縱橫比未滿2的球狀粒子、和縱橫比2以上的棒狀粒子為更佳。藉由含有此縱橫比2以上的棒狀粒子，可進一步提升耐蝕性。又，含有縱橫比3以上的棒狀粒子為最佳。In the present invention, it is preferred that the particles of the intermetallic compound (Mg 17 Al 12 or the like) contain spherical particles having an aspect ratio of less than 2. Here, the aspect ratio is expressed by the ratio of the major axis to the minor axis (long diameter/short diameter) of the particles. In particular, it is more preferable to contain spherical particles having an aspect ratio of less than 2 and rod-like particles having an aspect ratio of 2 or more. By including the rod-shaped particles having an aspect ratio of 2 or more, the corrosion resistance can be further improved. Further, it is preferable to include rod-shaped particles having an aspect ratio of 3 or more.
在本發明，上述的金屬間化合物(Mg17Al12等)的粒子中，球狀(縱橫比未滿2)的粒子的平均粒徑為0.4μm以上為佳。在此，平均粒徑係為求取板剖面的SEM觀察之觀察視野內的金屬間化合物的球狀粒子的數量，將存在於觀察視野內之該粒子的總和面積除以該粒子的數量的值視為每個圓形(球狀)的粒子之面積，再算出相等於此面積之圓的直徑之值。平均粒徑大較好，0.5μm以上為更佳。平均粒徑的上限未特別限定，但，當粗大的金屬間化合物的粒子存在過多時，則在進行塑性加工時容易產生破裂等，故，理想為5μm。In the present invention, in the particles of the above-mentioned intermetallic compound (such as Mg 17 Al 12 or the like), the spherical particles (having an aspect ratio of less than 2) preferably have an average particle diameter of 0.4 μm or more. Here, the average particle diameter is the number of spherical particles of the intermetallic compound in the observation field of the SEM observation of the cross section of the plate, and the total area of the particles existing in the observation field is divided by the number of the particles. Consider the area of each circular (spherical) particle and calculate the value of the diameter of the circle equal to this area. The average particle diameter is preferably large, and more preferably 0.5 μm or more. The upper limit of the average particle diameter is not particularly limited. However, when the particles of the coarse intermetallic compound are excessively large, cracking or the like is likely to occur during plastic working, and therefore, it is preferably 5 μm.
在本發明，具有優良的耐蝕性，鹽水噴霧實驗(依據JIS Z 2371：2000之實驗方法)之腐蝕減量為少。例如，能夠達到鹽水噴霧實驗96小時後的腐蝕減量為0.25 mg/cm2以下。腐蝕減量少為佳，0.20mg/cm2以下為更佳。在上述鹽水噴霧實驗，使用5%濃度的鹽水(溶解有鹽50g之1公升的水溶液)。In the present invention, it has excellent corrosion resistance, and the salt spray test (according to the experimental method of JIS Z 2371:2000) has less corrosion reduction. For example, it is possible to achieve a corrosion reduction of 0.25 mg/cm 2 or less after 96 hours of the salt spray test. The corrosion loss is preferably small, and 0.20 mg/cm 2 or less is more preferable. In the above salt spray test, a 5% concentration of brine (1 liter of an aqueous solution in which 50 g of salt was dissolved) was used.
本發明的鎂合金板，係可藉由例如，以下的本發明的製造方法來製造。本發明的鎂合金板的製造方法之特徵為具有以下的各製程。The magnesium alloy sheet of the present invention can be produced, for example, by the following production method of the present invention. The method for producing a magnesium alloy sheet of the present invention is characterized by having the following respective processes.
鑄造製程：藉由連續鑄造，來製造由含有添加元素之鎂合金所構成的鑄造材之製程。Casting process: A process of producing a cast material composed of a magnesium alloy containing an additive element by continuous casting.
熱處理製程：在將鑄造材保持於400℃以上後，以30℃/min以下的冷卻速度進行冷卻，來製作熱處理材製程。Heat treatment process: After the cast material is maintained at 400 ° C or higher, it is cooled at a cooling rate of 30 ° C / min or less to prepare a heat-treated material process.
輥軋製程：將熱處理材進行溫間輥軋，來製作輥軋板之製程。Roll rolling process: The heat-treated material is subjected to warm rolling to prepare a rolled sheet.
且，亦可具備有將上述輥軋板進行溫間矯正之矯正製程。Further, a correction process for correcting the temperature of the rolled sheet may be provided.
不易將鑄造材直接進行輥軋，熱處理製程係為了使鑄造材軟化，而在輥軋前進行。又，在熱處理製程，藉由保持在一定時間的預定溫度，能夠使鎂合金的組成均質化，並且亦具有使Al等的添加元素固溶於鎂合金中之效果。以往，由於在熱處理製程之冷卻過程中，當粗大的金屬間化合物(Mg17Al12等)的粒子大量析出時，則會造成耐蝕性降低，故，在例如將鑄造材保持於350℃以上後，再藉由水冷、風冷等予以強制冷卻。具體而言，為了快速通過金屬間化合物的析出速度大的溫度區域(350℃~250℃)，以100℃/min以上的冷卻速度將350℃~250℃的溫度區域冷卻(急冷)，獲得固溶體。但，經過本發明者們精心研究的結果得知，在熱處理製程，並非進行急冷，而是藉由以30℃/min以下的冷卻速度進行冷卻(徐冷)，最終可獲得具有優良耐蝕性之輥軋板(鎂合金板)。It is difficult to directly roll the cast material, and the heat treatment process is performed before the rolling in order to soften the cast material. Further, in the heat treatment process, the composition of the magnesium alloy can be homogenized by maintaining the predetermined temperature for a certain period of time, and the additive element such as Al can be solid-dissolved in the magnesium alloy. Conventionally, when a large amount of particles of a coarse intermetallic compound (Mg 17 Al 12 or the like) are precipitated during the cooling process of the heat treatment process, corrosion resistance is lowered. Therefore, for example, after the cast material is maintained at 350 ° C or higher, Then, forced cooling is performed by water cooling, air cooling, and the like. Specifically, in order to quickly pass through a temperature range (350 ° C to 250 ° C) in which the rate of precipitation of the intermetallic compound is large, the temperature region of 350 ° C to 250 ° C is cooled (quenched) at a cooling rate of 100 ° C / min or more to obtain a solid. Solution. However, as a result of intensive studies by the inventors, it has been found that, in the heat treatment process, cooling is not performed by quenching at a cooling rate of 30 ° C/min or less, and finally, excellent corrosion resistance can be obtained. Rolled sheet (magnesium alloy sheet).
以下，說明關於各製程。Hereinafter, each process will be described.
在鑄造製程，係藉由雙輥軋法等的連續鑄造法，製作預定組成的鑄造材。例如，能夠利用WO2006/003899所記載的連續鑄造技術。連續鑄造法係由於可進行急冷凝固，故，不僅可減低氧化物、偏析等，並且亦可抑制超過10μm之粗大的析出物(金屬間化合物)產生。鑄造材的厚度未特別限定，但，由於過厚過時容易產生偏析，故，10mm以下為佳，5mm以下為更佳。In the casting process, a cast material having a predetermined composition is produced by a continuous casting method such as a twin roll method. For example, the continuous casting technique described in WO2006/003899 can be utilized. Since the continuous casting method can be rapidly solidified, it is possible to reduce not only oxides, segregation, and the like, but also coarse precipitates (intermetallic compounds) exceeding 10 μm. The thickness of the cast material is not particularly limited. However, since segregation is likely to occur when the thickness is too large, 10 mm or less is preferable, and 5 mm or less is more preferable.
在熱處理製程，在將上述鑄造材保持於400℃以上後，以30℃/min以下的冷卻速度進行冷卻，來製作熱處理材。熱處理，可舉出加熱至400℃以上420℃以下、理想為410℃以下的溫度，在該狀態下保持60分鐘以上2400分鐘以下(1小時～40小時)。又，此保持時間係Al的含有量越多則越長為佳。另外，以30℃/min以下的冷卻速度進行冷卻之溫度區域，可舉出例如，400℃至250℃。更理想為如下述，分成400℃～350℃的溫度區域、和350℃～250℃的溫度區域，調節各溫度區域之冷卻速度。In the heat treatment process, after the cast material is held at 400 ° C or higher, it is cooled at a cooling rate of 30 ° C / min or less to prepare a heat-treated material. The heat treatment is carried out by heating to a temperature of 400 ° C or more and 420 ° C or less, preferably 410 ° C or less, and in this state, it is kept for 60 minutes or more and 2400 minutes or less (1 hour - 40 hours). Moreover, it is preferable that the retention time is such that the content of Al is longer. Further, the temperature region to be cooled at a cooling rate of 30 ° C / min or less may, for example, be 400 ° C to 250 ° C. More preferably, the temperature is divided into a temperature range of 400 ° C to 350 ° C and a temperature range of 350 ° C to 250 ° C as described below, and the cooling rate in each temperature region is adjusted.
從400℃到350℃，以30℃/min以下的冷卻速度進行冷卻，從350℃到250℃，以10℃/min以下的冷卻速度進行冷卻為佳。特別是在400℃～350℃的溫度區域，以2.0℃/min以下的冷卻速度進行冷卻為更佳，以0.2℃/min以下的冷卻速度進行冷卻為最佳。另外，在350℃～250℃的溫度區域，以1.0℃/min以下的冷卻速度進行冷卻為更佳。It is preferably cooled from 400 ° C to 350 ° C at a cooling rate of 30 ° C / min or less, and is preferably cooled from 350 ° C to 250 ° C at a cooling rate of 10 ° C / min or less. In particular, in a temperature range of 400 ° C to 350 ° C, it is more preferably cooled at a cooling rate of 2.0 ° C / min or less, and it is preferably cooled at a cooling rate of 0.2 ° C / min or less. Further, it is more preferably cooled at a cooling rate of 1.0 ° C / min or less in a temperature range of 350 ° C to 250 ° C.
如此，藉由將熱處理製程之冷卻條件作成為徐冷，能夠製造具有優良的耐蝕性輥軋板(鎂合金板)。具體而言，能夠製造出上述這樣的具有特定組成之鎂合金板。又，藉由調節在上述各溫度區域之冷卻速度，能夠控制金屬間化合物(Mg17Al12等)的析出狀態(具體而言，上述之XRD分析之金屬間化合物的主繞射面(4,1,1)繞射強度與Mg合金相的c面(0,0,2)繞射強度之比率、面積比率、粒子形態、及平均粒徑)，能夠謀求耐蝕性的提升。As described above, by subjecting the cooling conditions of the heat treatment process to cold cooling, it is possible to produce a rolled sheet (magnesium alloy sheet) having excellent corrosion resistance. Specifically, a magnesium alloy sheet having a specific composition as described above can be produced. Further, by adjusting the cooling rate in each of the temperature regions, it is possible to control the precipitation state of the intermetallic compound (Mg 17 Al 12 or the like) (specifically, the main diffraction surface of the intermetallic compound by XRD analysis described above (4, 1,1) The ratio of the diffraction intensity to the c-plane (0, 0, 2) diffraction intensity of the Mg alloy phase, the area ratio, the particle form, and the average particle diameter) can improve the corrosion resistance.
在輥軋製程，將上述熱處理材進行溫間輥軋，來製作輥軋板。在將熱處理材進行輥軋之際，藉由將材料(熱處理材，或進行最終輥軋前之輥軋途中的板材)進行加熱，能夠提高塑性加工性(輥軋加工性)。特別是當藉由將上述材料加熱至超過300℃時，則可充分地提高塑性加工性。但，當提高材料之加熱溫度，則在進行輥軋加工時，容易在材料產生燒結，或鎂母相的結晶粒粗大化並且大量產生粗大的金屬間化合物，造成最終的輥軋板的機械特性降低。因此，將輥軋製程之材料的加熱溫度作成為300℃以下。特別是材料的加熱溫度作成為150℃以上280℃以下為佳。又，藉由進行複數次(多道次(Multi pass))的輥軋，加工成期望的板厚(例如，0.3mm～3.0mm)，並且可將母相的平均結晶粒徑作小(例如，10μm以下，理想為5μm以下)，提高輥軋加工、沖壓加工之塑性加工性。輥軋係可利用習知的條件，例如，除了不僅材料亦將輥軋滾子予以加熱外，亦可將專利文獻1所記載的控制輥軋等予以組合並利用。In the roll rolling process, the heat-treated material was subjected to warm rolling to prepare a rolled sheet. When the heat-treated material is rolled, the plastic workability (rolling workability) can be improved by heating the material (heat-treated material or the plate material during the rolling process before the final rolling). In particular, when the above material is heated to more than 300 ° C, the plastic workability can be sufficiently improved. However, when the heating temperature of the material is increased, it is easy to cause sintering in the material during the rolling process, or the crystal grains of the magnesium matrix phase are coarsened and a large amount of coarse intermetallic compound is generated, resulting in mechanical properties of the final rolled sheet. reduce. Therefore, the heating temperature of the material of the roll rolling pass is made 300 ° C or less. In particular, the heating temperature of the material is preferably 150 ° C or more and 280 ° C or less. Further, by performing a plurality of (multi pass) rolling, it is processed into a desired sheet thickness (for example, 0.3 mm to 3.0 mm), and the average crystal grain size of the mother phase can be made small (for example, , 10 μm or less, preferably 5 μm or less), and improves the plastic workability in the rolling process and the press working. In the rolling system, the rolling conditions can be used in combination with, for example, not only the material but also the rolling rolls, and the controlled rolling described in Patent Document 1 can be used in combination.
又，在較包含輥軋製程之熱處理製程更後面的製程，將材料保持於150℃以上300℃以下的溫度區域之總和時間設成為12小時以下，並且控制上述材料的熱履歴，讓其不會被加熱超過300℃為佳。藉由控制保持在150℃～300℃的溫度區域之時間，能夠抑制金屬間化合物的過度成長(粗大化)。理想為將上述溫度區域設為150℃以上280℃以下，並控制成上述總和時間為6小時以下。Further, in a process further than the heat treatment process including the roll rolling process, the total time of the temperature region in which the material is maintained at 150 ° C or more and 300 ° C or less is set to 12 hours or less, and the heat trajectory of the above material is controlled so that it does not It is preferred to be heated above 300 °C. By controlling the time in the temperature range of 150 to 300 ° C, excessive growth (coarseness) of the intermetallic compound can be suppressed. It is preferable to set the temperature range to 150 ° C or more and 280 ° C or less, and control the total time to be 6 hours or less.
在進行多道次輥軋之情況，在保持於150℃～300℃的溫度區域之時間含於上述總和時間的範圍內，亦可在通過(pass)期間進行中間熱處理。藉由此中間熱處理，可將因至該中間熱處理前之塑性加工(主要為輥軋)所導入到材料之應變、殘留應力、集合組成等予以除去、減輕，在該中間熱處理後的輥軋，能夠防止不經意的破裂、應變、變形等，能夠進行更圓滑的輥軋。在進行中間熱處理之情況，也將材料的加熱溫度作成為300℃以下。此中間熱處理之理想的材料的加熱溫度係為250℃以上、280℃以下。In the case of performing multi-pass rolling, it is contained in the temperature range of 150 ° C - 300 ° C in the range of the above-mentioned total time, and intermediate heat treatment may be performed during the pass. By the intermediate heat treatment, the strain, the residual stress, the aggregate composition, and the like introduced into the material by the plastic working (mainly rolling) before the intermediate heat treatment can be removed and reduced, and the rolling after the intermediate heat treatment is performed. It is possible to prevent inadvertent cracking, strain, deformation, and the like, and to perform smoother rolling. In the case of performing the intermediate heat treatment, the heating temperature of the material is also made 300 ° C or lower. The heating temperature of the material for the intermediate heat treatment is 250 ° C or more and 280 ° C or less.
在矯正製程，在將上述輥軋板加熱至100℃以上300℃以下之狀態下進行矯正。在此情況，保持於150℃～300℃的溫度區域之時間也含於上述總和時間。亦可對藉由輥軋製程所製作的上述輥軋板實施如專利文獻1所記載的最終熱處理(最終退火)，但，當不進行此最終熱處理或在最終熱處理後再進行上述溫間矯正，則可提高沖壓加工之塑性加工性。矯正亦可使用如WO2009/001516所記載的輥軋整平器等，將輥軋板加熱至100℃以上300℃以下、理想為150℃以上280℃以下後進行為佳。當對進行有這樣的溫間矯正之輥軋板實施沖壓加工等之塑性加工時，由於在塑性加工時會產生動態再結晶化，故，容易進行塑性加工。In the correction process, the above-mentioned rolled sheet is heated to a temperature of 100 ° C or more and 300 ° C or less. In this case, the time of maintaining the temperature region of 150 ° C to 300 ° C is also included in the above total time. The final heat treatment (final annealing) described in Patent Document 1 may be performed on the above-described rolled sheet produced by a roll rolling process, but the above-described temperature correction may be performed after the final heat treatment is not performed or after the final heat treatment. The plastic workability of the press working can be improved. For the correction, it is preferable to use a roll flattener as described in WO2009/001516, and to heat the rolled sheet to 100 ° C or more and 300 ° C or less, preferably 150 ° C or more and 280 ° C or less. When plastic working such as press working is performed on a rolled sheet having such a temperature correction, dynamic recrystallization occurs during plastic working, so that plastic working is easy.
在進行上述最終熱處理之情況，能夠除去因輥軋加工導入到輥軋板之應變。最終熱處理係可舉出例如，將輥軋板加熱至100℃以上300℃以下的溫度，該狀態下保持5分鐘以上60分鐘以下。在此情況，保持於150℃～300℃的溫度區域之時間也含於上述總和時間。在此，專利文獻1雖記載有將加熱溫度作成為300℃～340℃，但，為了盡可能地抑制母相的結晶粒成長，在提高加熱溫度之情況，縮短加熱時間(例如未滿30分鐘)為佳。In the case where the above final heat treatment is performed, the strain introduced into the rolled sheet by the rolling process can be removed. In the final heat treatment, for example, the rolled sheet is heated to a temperature of 100 ° C or more and 300 ° C or less, and in this state, it is kept for 5 minutes or longer and 60 minutes or shorter. In this case, the time of maintaining the temperature region of 150 ° C to 300 ° C is also included in the above total time. Here, Patent Document 1 describes that the heating temperature is 300° C. to 340° C. However, in order to suppress the growth of crystal grains of the mother phase as much as possible, the heating time is shortened (for example, less than 30 minutes). ) is better.
又，對藉由上述製造方法所獲得的輥軋板(本發明的鎂合金板)實施沖壓加工之塑性加工，獲得鎂合金構件。塑性加工係當在200℃以上300℃以下的溫度區域進行時，可提高鎂合金板的塑性加工性進而容易進行塑性加工。在塑性加工時，將鎂合金板保持於200℃～300℃之時間非常短，例如在沖壓加工為60秒以下，這是因為實質上不會產生金屬間化合物的粗大化等的缺失之故。Moreover, the rolled sheet (the magnesium alloy sheet of the present invention) obtained by the above-described production method is subjected to press working plastic working to obtain a magnesium alloy member. When the plastic working is performed in a temperature range of 200 ° C or more and 300 ° C or less, the plastic workability of the magnesium alloy sheet can be improved and the plastic working can be easily performed. In the plastic working, the magnesium alloy sheet is kept at a temperature of from 200 ° C to 300 ° C for a very short period of time, for example, press working for 60 seconds or less, because substantially no loss of the intermetallic compound is caused.
又，在上述塑性加工後實施完成熱處理，能夠謀求因塑性加工所導入至鎂合金構件之應變、殘留應力的去除、機械特性的提升。完成熱處理係可舉出與上述最終熱處理相同條件(加熱溫度：100℃～300℃、加熱小時：5分鐘～60分鐘)。但，在此情況，保持於150℃～300℃的溫度區域之時間也含於上述總和時間為佳。Moreover, after performing the heat treatment after the plastic working, the strain introduced into the magnesium alloy member by plastic working, the removal of the residual stress, and the improvement of the mechanical properties can be achieved. The completion of the heat treatment is the same as the above final heat treatment (heating temperature: 100 ° C to 300 ° C, heating time: 5 minutes to 60 minutes). However, in this case, the time to maintain the temperature region of 150 ° C to 300 ° C is also preferably included in the above total time.
且，上述塑性加工後，亦可為了鎂合金構件之保護、美感(意匠性)、耐蝕性的提升等之目的，對鎂合金構件實施塗裝。Further, after the plastic working, the magnesium alloy member may be coated for the purpose of protection, aesthetics, and corrosion resistance of the magnesium alloy member.
本發明的鎂合金板係藉由具有板表面的XRD分析之金屬間化合物的主繞射面(4,1,1)繞射強度除以Mg合金相的c面(0,0,2)繞射強度之比率為0.040以上的組成，而具有優良的耐蝕性。又，本發明的鎂合金板的製造方法係藉由將熱處理製程之冷卻條件作成為冷卻速度30℃/min以下的徐冷，能夠製造具優良的耐蝕性之鎂合金板。The magnesium alloy sheet of the present invention is obtained by dividing the diffraction intensity of the main diffraction surface (4, 1, 1) of the intermetallic compound having the XRD analysis of the surface of the sheet by the c-plane (0, 0, 2) of the Mg alloy phase. The ratio of the incident intensity is 0.040 or more, and has excellent corrosion resistance. Further, in the method for producing a magnesium alloy sheet according to the present invention, the cooling condition of the heat treatment process is set to a cooling rate of 30 ° C / min or less, whereby a magnesium alloy sheet having excellent corrosion resistance can be produced.
以下，說明關於本發明的實施形態。Hereinafter, embodiments of the present invention will be described.
使熱處理製程之冷卻條件不同，製造組成不同之各種鎂合金板，針對各板的組成、及耐蝕性進行評價。The cooling conditions of the heat treatment process were different, and various magnesium alloy sheets having different compositions were produced, and the composition and corrosion resistance of each of the sheets were evaluated.
在此實驗，準備利用以下的方式所製造之試料No.1～4的鎂合金板。In this experiment, a magnesium alloy sheet of Sample Nos. 1 to 4 produced by the following method was prepared.
雙輥軋連續鑄造法，製作由具有相當AZ91合金之組成(9.0%Al-1.0%Zn-0.15%～0.5%Mn(全部為質量%)、殘餘部分Mg)的鎂合金所構成的鑄造材(厚度：4mm)複數片。在此，試料No.1、3及4係製作長條狀鑄造材再捲繞成線圈狀之線圈材。試料No.2係作成為將鑄造材裁斷成預定長度的薄片狀之薄片材。A two-roll continuous casting method is used to produce a cast material composed of a magnesium alloy having a composition of AZ91 alloy (9.0% Al-1.0% Zn-0.15%-0.5% Mn (all mass%), residual Mg). Thickness: 4mm) Multiple pieces. Here, Sample Nos. 1, 3, and 4 are formed into a coil-shaped coil material in which a long cast material is produced. Sample No. 2 is a sheet-like sheet material obtained by cutting a cast material into a predetermined length.
接著，將各鑄造材(線圈材或薄片材)放入到熱處理爐，在400℃下保持24小時，再以表1所示的條件進行冷卻，製作熱處理材。再者，表1中的冷卻速度，在線圈材為測定線圈材的表面溫度，在薄片材為測定薄片材的表面溫度後所求得的值。Next, each cast material (coil material or sheet material) was placed in a heat treatment furnace, and kept at 400 ° C for 24 hours, and then cooled under the conditions shown in Table 1, to prepare a heat-treated material. In addition, the cooling rate in Table 1 is a value obtained by measuring the surface temperature of the coil material in the coil material and measuring the surface temperature of the sheet material in the sheet material.
在此，試料No.1係將從熱處理爐所取出的線圈材在該狀態下置入到水槽，藉由水冷，從400℃強制冷卻至250℃為止。試料No.2係將熱處理爐所取出的薄片材置入到進行溫度調節之恆溫室，藉由空冷，從400℃冷卻到350℃後，再置入到設定成更低的溫度之其他恆溫室，藉由空冷，從350℃冷卻到250℃。試料No.3係將從熱處理爐所取出的線圈材在該狀態下進行放置，從400℃自然冷卻到250℃。試料No.4係在停止加熱後的熱處理爐內將線圈材直接放置，從400℃自然冷卻到350℃後，再從熱處理爐取出線圈材，在該狀態下放置，使其從350℃自然冷卻到250℃。Here, in the sample No. 1, the coil material taken out from the heat treatment furnace was placed in a water tank in this state, and was forcibly cooled from 400 ° C to 250 ° C by water cooling. In sample No. 2, the sheet material taken out from the heat treatment furnace was placed in a thermostatic chamber for temperature adjustment, cooled from 400 ° C to 350 ° C by air cooling, and then placed in another constant temperature chamber set to a lower temperature. Cooled from 350 ° C to 250 ° C by air cooling. In the sample No. 3, the coil material taken out from the heat treatment furnace was placed in this state, and naturally cooled from 400 ° C to 250 ° C. In sample No. 4, the coil material was placed directly in the heat treatment furnace after the heating was stopped, and the coil material was naturally cooled from 400 ° C to 350 ° C, and then the coil material was taken out from the heat treatment furnace, and placed in this state to be naturally cooled from 350 ° C. To 250 ° C.
其次，以下述條件，對各熱處理材進行多道次輥軋，製作輥軋板(厚度：大約0.6mm)。Next, each heat-treated material was subjected to multi-pass rolling under the following conditions to prepare a rolled sheet (thickness: about 0.6 mm).
壓下率：5%/道(pass)～40%/道Reduction rate: 5% / pass ~ 40% / way
材料的加熱溫度：250℃～280℃Heating temperature of material: 250 ° C ~ 280 ° C
輥軋滾子之加熱溫度：100℃～250℃Rolling roller heating temperature: 100 ° C ~ 250 ° C
且，在將各輥軋板加熱到200℃之狀態下進行溫間矯正。溫間矯正係使用輥軋整平裝置來進行，其該整平裝置具有：用來加熱輥軋板之加熱爐；和具有對被加熱爐所加熱的輥軋板連續地賦予彎曲(傾斜)之複數個滾子之滾子部。滾子部係具備有上下相對向並配置成鋸齒狀的複數個滾子。輥軋整平裝置係一邊將輥軋板在加熱爐內加熱一邊輸送至滾子部，在每次通過滾子部的上下滾子間時，藉由這些滾子，依次對輥軋板賦予彎曲。Further, the temperature correction was performed while heating each of the rolled sheets to 200 °C. The inter-warm correction is performed using a roll leveling device having: a heating furnace for heating the rolled sheet; and having a rolling (tilting) continuously applied to the rolled sheet heated by the heating furnace The roller part of a plurality of rollers. The roller unit includes a plurality of rollers that are vertically opposed to each other and arranged in a zigzag shape. The roll flattening device transports the rolled sheet to the roller portion while heating in the heating furnace, and sequentially bends the rolled sheet by the rollers each time passing between the upper and lower rollers of the roller portion. .
最後，對進行了溫間矯正之輥軋板，藉由#600的研磨帶實施濕式帶式研磨，將輥軋板的表面予以平滑化，並且將輥軋板的厚度調整成0.6mm。再者，在熱處理製程之後的製程，控制熱履歴，來將保持於150℃～300℃的溫度區域之總和時間作成為12小時以下，並且不會加熱到超過300℃的溫度。Finally, the rolled sheet subjected to the temperature correction was subjected to wet belt grinding by a #600 belt, the surface of the rolled sheet was smoothed, and the thickness of the rolled sheet was adjusted to 0.6 mm. Further, in the process after the heat treatment process, the heat trajectory is controlled so that the total time of the temperature region maintained at 150 ° C to 300 ° C is made 12 hours or less, and is not heated to a temperature exceeding 300 ° C.
從如以上的方式所製作的各輥軋板切出一部分，獲得試料No.1～4的鎂合金板。A part of each of the rolled sheets produced as described above was cut out to obtain magnesium alloy sheets of Sample Nos. 1 to 4.
針對各試料，進行板表面的XRD(X-Ray Diffraction)分析，分別測定顯示板表面的XRD分析之金屬間化合物(Mg17Al12)的主繞射面(4,1,1)繞射強度、及Mg合金相的c面(0,0,2)繞射強度之計算數。藉由前者除以後者，求取繞射強度的比率。XRD分析係使用飛利浦社製之多機能X線繞射裝置X’pertPRO。又，XRD分析的條件係如以下所述。各試料之繞射強度的比率顯示於表2。For each sample, XRD (X-Ray Diffraction) analysis of the surface of the plate was performed to measure the diffraction intensity of the main diffraction surface (4, 1, 1) of the intermetallic compound (Mg 17 Al 12 ) by XRD analysis on the surface of the display panel. And the calculation of the diffraction intensity of the c-plane (0, 0, 2) of the Mg alloy phase. The ratio of the diffraction intensity is obtained by dividing the former by the former. The XRD analysis uses a multi-functional X-ray diffraction device X'pertPRO manufactured by Philips. Further, the conditions of XRD analysis are as follows. The ratio of the diffraction intensity of each sample is shown in Table 2.
使用X線：Cu-KαUse X-ray: Cu-Kα
激勵條件：45kV，40mAExcitation conditions: 45kV, 40mA
受光光學系統：蘇萊爾調焦狹縫系統(Soller-slit system)Receiving optics: Soller-slit system
掃描方法：θ-2θ掃描Scanning method: θ-2θ scan
測定範圍：2θ=20°～50°(步寬：0.03°)Measuring range: 2θ=20°～50° (step width: 0.03°)
積算小時：1secTotal hours: 1sec
針對各試料，藉由使用Ar離子光束的截面拋光儀，沿著與輥軋方向呈正交的方向，朝板厚方向進行剖面露出加工，對該剖面進行SEM(Scanning Electron Microscope)觀察。SEM觀察係使用Carl Zeiss社製之低加速電壓掃描型電子顯微鏡Ultra55。又，SEM觀察之條件為加速電壓5kV、試料無塗佈。觀察係以鏡內像進行。在此，圖1係試料No.1的SEM照片、圖2係試料No.3的SEM照片、圖3係試料No.4的SEM照片。在圖1～3中，淡灰色的粒子為金屬間化合物(Mg17Al12)。再者，圖中的縱方向可看到之條紋係為剖面露出加工之痕跡。For each sample, a cross-section polisher using an Ar ion beam was used to perform cross-sectional exposure processing in a direction perpendicular to the rolling direction in the direction of the sheet thickness, and the cross-section was observed by SEM (Scanning Electron Microscope). The SEM observation was performed using a low acceleration voltage scanning electron microscope Ultra55 manufactured by Carl Zeiss. Further, the conditions under SEM observation were an acceleration voltage of 5 kV, and the sample was not coated. The observation is performed with an intraocular image. Here, FIG. 1 is an SEM photograph of Sample No. 1, FIG. 2 is an SEM photograph of Sample No. 3, and FIG. 3 is an SEM photograph of Sample No. 4. In Figs. 1 to 3, the light gray particles are intermetallic compounds (Mg 17 Al 12 ). Further, the stripe visible in the longitudinal direction in the figure is a trace of the cross-section exposed processing.
針對各試料，求取板剖面的SEM觀察之金屬間化合物(Mg17Al12)的面積比率。在此，進行5次的剖面露出加工，針對5個剖面，分別視察任意的3個視野，在每個觀察視野，調查存在於觀察視野內之所有的金屬間化合物的粒子的面積，算出總和面積。又，在總計15個觀察視野，分別求取金屬間化合物的總和面積除以觀察視野面積之比率，將該平均值作為面積比率。再者，觀察視野尺寸係設為4μm×6μm(面積：24μm2)，觀察視野係選擇棒狀(縱橫比2以上)的粒子未存在之區域，即，僅球狀(縱橫比未滿2)的粒子存在之區域。各試料之面積比率(%)顯示於表2。The area ratio of the intermetallic compound (Mg 17 Al 12 ) observed by SEM of the plate cross section was determined for each sample. Here, the cross-sectional exposure processing was performed five times, and three arbitrary visual fields were inspected for each of the five cross-sections, and the area of the particles of all the intermetallic compounds existing in the observation visual field was examined for each observation visual field, and the total area was calculated. . Further, in a total of 15 observation fields, the ratio of the total area of the intermetallic compound divided by the area of the observation field was determined, and the average value was defined as an area ratio. In addition, the observation visual field size was set to 4 μm × 6 μm (area: 24 μm 2 ), and the field of view was selected as a region in which rods (having an aspect ratio of 2 or more) were not present, that is, only spherical (the aspect ratio was less than 2). The area where the particles exist. The area ratio (%) of each sample is shown in Table 2.
又，同樣地藉由板剖面的SEM觀察，求取金屬間化合物(Mg17Al12)的球狀(縱橫比未滿2)的粒子的平均粒徑。在此，在上述的觀察視野，針對每個觀察視野，調查存在於觀察視野內之所有的球狀粒子的數量。在總計15個觀察視野，算出金屬間化合物的上述總和面積除以該粒子的數量之面積，求取相等於此面積之圓的直徑，將該平均值作為平均粒徑。各試料之平均粒徑(μm)顯示於表2。Further, in the same manner, the average particle diameter of the spherical (form of aspect ratio less than 2) particles of the intermetallic compound (Mg 17 Al 12 ) was determined by SEM observation of the cross section of the sheet. Here, in the above-described observation field of view, the number of all the spherical particles existing in the observation field of view is investigated for each observation field of view. In a total of 15 observation fields, the total area of the intermetallic compound was calculated by dividing the area of the number of the particles, and the diameter of a circle equivalent to the area was determined, and the average value was defined as the average particle diameter. The average particle diameter (μm) of each sample is shown in Table 2.
進一步，藉由板剖面的SEM觀察，調查金屬間化合物(Mg17Al12)的粒子形態。在此，在任意1個觀察視野(其中，觀察視野尺寸：120μm×90μm)，藉由目視，判斷存在於觀察視野內之金屬間化合物的粒子的形狀。其結果，試料No.1及No.2僅存在縱橫比未滿2的球狀粒子。另外，試料No.3及No.4中，係縱橫比未滿2的球狀粒子與縱橫比2以上的棒狀粒子混合存在著。又，關於試料No.3及No.4，進行縱橫比2以上的棒狀粒子的存在比率之比較，確認到比起試料No.3，試料No.4存在有多數縱橫比2以上的棒狀粒子。具體而言，在試料No.3，每1個觀察視野，存在有3個以上的棒狀粒子，而在試料No.4，每1個觀察視野，存在有5個以上的棒狀粒子。又，在試料No.3及No.4所確認到的棒狀粒子，幾乎為縱橫比3以上。Further, the particle morphology of the intermetallic compound (Mg 17 Al 12 ) was investigated by SEM observation of the cross section of the sheet. Here, the shape of the particles of the intermetallic compound existing in the observation field of view is determined by visual observation in any one of the observation fields (here, the observation field size: 120 μm × 90 μm). As a result, in the samples No. 1 and No. 2, only spherical particles having an aspect ratio of less than 2 were present. Further, in samples No. 3 and No. 4, spherical particles having an aspect ratio of less than 2 were mixed with rod-shaped particles having an aspect ratio of 2 or more. In addition, in the sample No. 3 and No. 4, the ratio of the presence ratio of the rod-shaped particles having an aspect ratio of 2 or more was compared, and it was confirmed that the sample No. 4 had a rod shape having a plurality of aspect ratios of 2 or more as compared with the sample No. 3. particle. Specifically, in sample No. 3, three or more rod-shaped particles were present per observation field, and in sample No. 4, five or more rod-shaped particles existed per observation field. Further, the rod-shaped particles confirmed in Sample No. 3 and No. 4 had an aspect ratio of almost 3 or more.
針對各試料，進行鹽水噴霧實驗，求取腐蝕減量。在此，藉由依據JIS Z 2371：2000之實驗方法進行。鹽水噴霧實驗係使用SUGA試驗機(股)製的鹽水噴霧實驗機CY-90。又，鹽水噴霧實驗之條件係設為實驗溫度35℃、鹽水濃度5%、實驗時間96小時。各試料之腐蝕減量(mg/cm2)顯示於表2。For each sample, a salt spray test was performed to obtain a corrosion reduction. Here, it is carried out by an experimental method in accordance with JIS Z 2371:2000. The salt spray test was carried out using a saline spray test machine CY-90 manufactured by a SUGA test machine. Further, the conditions of the salt spray test were set to an experimental temperature of 35 ° C, a brine concentration of 5%, and an experimental time of 96 hours. The corrosion loss (mg/cm 2 ) of each sample is shown in Table 2.
腐蝕減量係以下述方式進行測定。從試料No.1～No.4分別採取實驗片，測定各實驗片之質量(實驗前質量)。將各實驗片安裝於鹽水噴霧實驗機之實驗槽內，進行96小時之鹽水噴霧實驗。在實驗結束後，從實驗槽取出各實驗片，除去各實驗片的腐蝕生成物。腐蝕生成物的除去，首先準備在氧化鉻(VI)100g、鉻酸銀10g添加蒸餾水所成的溶液1000ml，對作成為煮沸狀態之此溶液浸漬各實驗片1分鐘，除去腐蝕生成物。進一步準備在氧化鉻(VI)200g、鉻酸銀10g、硫酸鋇20g添加蒸餾水所成的溶液1000ml，對作成為20℃～25℃之此溶液浸漬各實驗片1分鐘浸漬，除去腐蝕生成物。然後，在以刷子等除去各實驗片表面的附著物後，以水清洗各實驗片並予以乾燥。在除去各實驗片的腐蝕生成物後，測定各實驗片的質量(實驗後質量)。又，將從實驗前質量減去實驗後質量之質量除以各實驗片的面積的值作為腐蝕減量。再者，質量之測定，係使用(股)島津製作所製的電子分析天秤AEU-210。The corrosion reduction was measured in the following manner. Test pieces were taken from samples No. 1 to No. 4, and the mass (pre-experimental mass) of each test piece was measured. Each test piece was placed in an experimental tank of a salt spray test machine, and a salt spray test for 96 hours was performed. After the end of the experiment, each test piece was taken out from the experimental tank, and the corrosion product of each test piece was removed. For the removal of the corrosion product, 1000 ml of a solution prepared by adding distilled water to 100 g of chromium (VI) oxide and 10 g of silver chromate was prepared, and each of the test pieces was immersed in the boiling state for 1 minute to remove the corrosion product. Further, 1000 ml of a solution prepared by adding distilled water to 200 g of chromium (VI) oxide, 10 g of silver chromate, and 20 g of barium sulfate was prepared, and each of the test pieces which were prepared at 20 ° C to 25 ° C was immersed for 1 minute to be immersed to remove the corrosion product. Then, after removing the deposit on the surface of each test piece with a brush or the like, each test piece was washed with water and dried. After the corrosion product of each test piece was removed, the mass (test mass) of each test piece was measured. Further, the value of the mass after the experiment was subtracted from the mass of the area of each test piece from the mass before the experiment as the corrosion loss. In addition, the mass measurement was performed using the electronic analysis scale AEU-210 manufactured by Shimadzu Corporation.
從表2的結果可得知，XRD分析之金屬間化合物(Mg17Al12)的主繞射面(4,1,1)繞射強度與Mg合金相的c面(0,0,2)繞射強度之比率為0.040以上的試料No.2～4，其進行鹽水噴霧實驗96小時後的腐蝕減量為0.25 mg/cm2以下，比起試料No.1，具有優良的耐蝕性。又，從耐蝕性的觀點來看可得知，板剖面的SEM觀察之金屬間化合物(Mg17Al12)的面積比率為10%以上、金屬間化合物(Mg17Al12)的粒子的平均粒徑為0.4μm以上為佳。特別是含有棒狀金屬間化合物(Mg17Al12)的粒子之試料No.3及No.4，進行鹽水噴霧實驗96小時後的腐蝕減量為0.20mg/cm2以下，具有更優良之耐蝕性。From the results in Table 2, the diffraction surface of the main diffraction surface (4, 1, 1) of the intermetallic compound (Mg 17 Al 12 ) by XRD analysis and the c-plane of the Mg alloy phase (0, 0, 2) Sample Nos. 2 to 4 in which the ratio of the diffraction intensity was 0.040 or more, and the corrosion loss after the salt spray test for 96 hours was 0.25 mg/cm 2 or less, and the corrosion resistance was excellent compared with the sample No. 1. Moreover, from the viewpoint of corrosion resistance, the area ratio of the intermetallic compound (Mg 17 Al 12 ) observed by SEM of the plate cross section is 10% or more, and the average particle of the intermetallic compound (Mg 17 Al 12 ) The diameter is preferably 0.4 μm or more. In particular, samples No. 3 and No. 4 containing particles of a rod-shaped intermetallic compound (Mg 17 Al 12 ) were subjected to a salt spray test for 96 hours, and the corrosion loss was 0.20 mg/cm 2 or less, thereby providing more excellent corrosion resistance. .
由以上的結果得知，以特定條件所製造的鎂合金板呈現優良的耐蝕性。具體而言，將熱處理製程之冷卻條件設成為冷卻速度30℃/min以下的徐冷之試料No.2～4，比起與從來同樣地進行急冷之試料No.1，具有優良的耐蝕性。又可得知，將400℃～350℃的溫度區域以30℃/min以下的冷卻速度，而將350℃～250℃的溫度區域以10℃/min以下的冷卻速度各自進行冷卻為佳。特別是400℃～350℃的溫度區域以2.0℃/min以下的冷卻速度、350℃～250℃的溫度區域以1.0℃/min以下的冷卻速度各自冷卻之試料No.3及No.4，具有更為優良之耐蝕性。From the above results, it is known that the magnesium alloy sheet produced under specific conditions exhibits excellent corrosion resistance. Specifically, the cooling conditions of the heat treatment process were set to Sample Nos. 2 to 4 of Cooling at a cooling rate of 30° C./min or less, and had excellent corrosion resistance as compared with Sample No. 1 which was quenched in the same manner as before. Further, it is preferable that the temperature region of 400 ° C to 350 ° C is cooled at a cooling rate of 30 ° C / min or less, and the temperature region of 350 ° C to 250 ° C is cooled at a cooling rate of 10 ° C / min or less. In particular, Sample No. 3 and No. 4 each having a cooling rate of 2.0° C./min or less and a cooling zone of 350° C. to 250° C. at a cooling rate of 1.0° C./min or less in a temperature range of 400° C. to 350° C. More excellent corrosion resistance.
再者，本發明不限於上述實施形態者，在不超出本發明的技術思想範圍內可進行適宜變更。例如，可適宜變更鎂合金的組成、鎂合金板的製造條件等。In addition, the present invention is not limited to the above-described embodiments, and can be appropriately modified without departing from the scope of the technical idea of the present invention. For example, the composition of the magnesium alloy, the production conditions of the magnesium alloy sheet, and the like can be appropriately changed.
本發明的鎂合金板，可理想地利用於電氣、電子機器類的各種構件、特別是手機、筆記型電腦之攜帶用機器的框體外，亦可理想地利用於被要求耐蝕性之各種構件。又，本發明的鎂合金板的製造方法係可理想地利用於被要求耐蝕性之鎂合金板的製造。The magnesium alloy sheet of the present invention can be suitably used for various members of electric and electronic equipment, in particular, a casing of a mobile phone or a notebook computer, and can be preferably used for various members requiring corrosion resistance. Moreover, the method for producing a magnesium alloy sheet of the present invention can be preferably used for the production of a magnesium alloy sheet which is required to have corrosion resistance.
圖1係試料No.1的鎂合金板的剖面的SEM照片。Fig. 1 is a SEM photograph of a cross section of a magnesium alloy sheet of sample No. 1.
圖2係試料No.3的鎂合金板的剖面的SEM照片。Fig. 2 is a SEM photograph of a cross section of a magnesium alloy sheet of sample No. 3.
圖3係試料No.4的鎂合金板的剖面的SEM照片。Fig. 3 is a SEM photograph of a cross section of a magnesium alloy sheet of sample No. 4.
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| JP4127126B2 (en) * | 2003-06-10 | 2008-07-30 | 住友金属工業株式会社 | Magnesium alloy plate manufacturing method |
| US7841380B2 (en) | 2004-06-30 | 2010-11-30 | Sumitomo Electric Industries, Ltd. | Producing method for magnesium alloy material |
| JP4253847B2 (en) * | 2004-11-30 | 2009-04-15 | 住友電気工業株式会社 | Magnesium alloy wire, method for producing the same, and magnesium alloy molded body |
| JP4730601B2 (en) * | 2005-03-28 | 2011-07-20 | 住友電気工業株式会社 | Magnesium alloy plate manufacturing method |
| CN102191418B (en) | 2007-06-28 | 2013-08-14 | 住友电气工业株式会社 | Magnesium alloy plate, its manufacturing method, and worked member |
| CN102197152B (en) * | 2008-10-22 | 2013-11-13 | 住友电气工业株式会社 | Formed product of magnesium alloy and magnesium alloy sheet |
| JP2010209452A (en) | 2009-03-12 | 2010-09-24 | Sumitomo Electric Ind Ltd | Magnesium alloy member |
-
2011
- 2011-11-08 KR KR1020137009936A patent/KR101799615B1/en active IP Right Grant
- 2011-11-08 EP EP11842319.3A patent/EP2641986B1/en not_active Not-in-force
- 2011-11-08 CN CN201180055334.3A patent/CN103210102B/en active Active
- 2011-11-08 WO PCT/JP2011/075757 patent/WO2012066986A1/en active Application Filing
- 2011-11-08 US US13/882,785 patent/US9222161B2/en active Active
- 2011-11-15 TW TW100141646A patent/TWI529251B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9900943B2 (en) | 2016-05-23 | 2018-02-20 | On-Bright Electronics (Shanghai) Co., Ltd. | Two-terminal integrated circuits with time-varying voltage-current characteristics including phased-locked power supplies |
Also Published As
| Publication number | Publication date |
|---|---|
| US9222161B2 (en) | 2015-12-29 |
| CN103210102B (en) | 2015-11-25 |
| EP2641986A4 (en) | 2017-09-06 |
| EP2641986A1 (en) | 2013-09-25 |
| KR101799615B1 (en) | 2017-11-20 |
| KR20130122943A (en) | 2013-11-11 |
| US20130220496A1 (en) | 2013-08-29 |
| WO2012066986A1 (en) | 2012-05-24 |
| TW201233815A (en) | 2012-08-16 |
| EP2641986B1 (en) | 2019-01-23 |
| CN103210102A (en) | 2013-07-17 |
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